Process of making phenylglycin salts.



KARL soHm'rzsrAHN, or orrnnBAcH-oN-rnE-MAIN, GERMANY, assm ori s CORPORATION OF cnnmscnn FABRIK. omnsnnm ELEKTRON, or rnanx'ronr-on l THE-MAIN, GERMANY.

PROCESS OF MAKme rHnnYLenYcm saws.

No Drawing.

Specification of Letters Patent.

useful Improvements in Processes of Makin'g Phenyl-glycin Salts, ofwhich the following is a specification.

No process has hitherto been known for. directly producing 'phenylglycin' salt of high percentage and free from alkalichlorid,

(as is necessary for making indoxyl-melts), from phenylglycin-n elts, obtained by reacting with approximately three or more molecular proportions of anilin upon one molecular' proportion of chloracetic acid, which melts contain besides phenylglycin (inform of its anilin salt) phenylglycinanilid. In working up such melts, two processes have been known hitherto. According to the one process the phenylglycinanilid is filtered olf after rendering the melt alkalin and afterv distilling off the anilin, and the. free phenylglycin is precipitated from the fil trate by means of acids. In this process a separate working up of the phenylglycinanilid is necessary, whereby considerable losses are. sustainedlbythe solubility of the phenylglycin in water, According to the other process, described in Letters Patent 818341, the production of phenylglycin salts is performed with advantage in such manner that the entire obtained, phenylglycin is converted into, its anilid which is separated and split oil by saponification, whereby losses of phenylglycin and the separate working up .of the anilid are avoided. I

, I'have found a new process by which high percented salts of phenylglycin free ,of alkali chlorid in good yields are obtained directly from melts, containing, phenylglycin (inform of anilin salt) besides phenylglycin anilid and hydrochlorid of anilin. In carrying out my process it is not necessary to transform asthitherto the formed phenylglycin into the-'anilid by atroublesome process which, as described in the specification of American Letters Patent in vacuo, It is also not necessary't sepsis Worlr'e rate the anilid and the glycin anjd them up n separate processes.

. nt ll selz-l ll" Application filed February 4, 1911. Serial No. 608,603. i 1- l i The new process is based .onthe-fac ,lthat,

" by addition of one equivalent proportion of a neutralizing agent, like an alkali :..hy.= :droxid, an earth-alkali-hydroxid, an: earth alkali-oxid or a carbonate of the aforesaid;

bases for instance, to onev molecular'propom tion of chlo-ra cetic acid used in the melt,

obtained by reacting upon one ,cmolecular.

proportion of chloracetic acid with approxil mative three molecular proportionsofanilin or more the alkali, earth alkali or carbonate exclusively reacts upon the hydrochlorid lofanilin which is formed in :the process ac cording to the chemical equation:

CICH2COOH+3CGHQNHY= The neutralizing agent does hotreactpl same time and does-not transform itinto the alkali salt of phenylaminoacetic acid.

tpheriylglycin-(in form of anilin salt besides phenylglycin anilid and hydrochlorid of anilin ,by a veryv simple and profitable proc-a ess salts pf phenylglycin free of alkali chlorid by addition of approxim-ative one said bases.

Owing to this smooth transformation itis posslble to obtain from melts, containing I The anilin set free from hydrochloridlof; g.

anilinby IIIBELIIS'Of alkali, actsin opportune manner-as solvent forthe phenylglyc-im anilin salt and anilid;v Therefore the oily and anilin-can easily be separated from the i590 mixture of phenylglycinanilin salt, anilid" formed alkalichlorid and can be obtained free of alkalichlorid, only small quantities of phenylglycinalkali remaining mixed with alkali-chloride The separated .oily' mixture maybe transformed into a salt 'Of'phenylQ glycin by heating it up to about 1305C, under pressure or without by means of overheated steam together with concentrated caustic alkali lye the proportion of which is calculated to the amount of phenylglycinanilin salt and anilicl contained in the mixture. After distilling off the excess of anilin by means of steam the phenylglycin salt is obtained in pure condition and good yield.

The new process may be performed in the following manner: For instance the alkali" or'earth alkali-hydroxid, earth alkali oxid or carbonate of the aforesaid bases is introduced in powdered condition into the ready melt. The resulting alkali-chlorid is filtered oif in case of being insoluble in the melt. If the alkali chlorid is dissolved in the melt, like calcium-chlorid for instance, water is added and the aqueous solution of the alkalichlorid filtered off from the mixture of anilin, phenylglycinanilin salt and anilid or an aqueous solution or suspension of the alkali or earth-alkali hydroxid or carbonate is added to the melt or the ready melt is poured into the alkaline solution or suspension.

The following examples will serve to show how my invention can be carried into practical 'effect; but my invention is not confined to these examples. The parts are by weight. I

Example I: To a melt, obtained by heating together 350 parts of anilin 100 parts of chloracetic acid and 200 parts of xylene up to about 130. (1., whereby about 100 parts of phenylglycinanilin salt and 119 parts of anilid are obtained, are poured at a temperature of 90 to 95 0., while stirring 350 parts of a lye containing 11.8 per cent. of caustic soda. The oil is separated from the hot aqueous sodium" chlorid-solution and directly transformed into phenylglycin potassium by means of 109parts of a lye containing 50 per cent. of caustic potash. Instead of caustic sodium lye may be used with the same result other alkali or earth alkali metal compounds, like sodium carbonate, potassium carbonate, caustic potassium lye, ammonia, slaked lime, or calcium carbonate for instance.

Example II: To a hot melt, obtained from 500 parts of anilin and 100 parts of chloracetic acid at 150 C., containing about 52 parts of phenylglycinanilin salt and 161 parts of anilid are poured while stirring 350 parts of a'suspension of slaked lime, containing 29.6 parts of calcium oxid. As soon as the reaction of the calcium hydroxid upon the hydrochlorate of anilin is completed the formed oil is separated from the hot aqueous calcium-chlorid solution and directly transformed into phenylglycin potassium 'by means of 110 parts of a solution containing 50 per cent. of caustic potash. Instead of slaked lime other alkali or earthalkali metal compounds may be used with Y the same result, or 29.6 parts of powdered calcium oxid may be added to the melt and "the necessary amount ofwater poured in afterward.

Example III: Into a hot melt obtained from 500 parts of anilin and 100 parts of chloracetic acid about at 120 C. containing about 135 parts of phenylglycinanilin salt and 88 parts of anilid are introduced 61 parts of calcined sodium carbonate. As soon as the reaction of the carbonate upon the hydrochlorid of anilin is completed the formed sodium-chlorid is filtered off from the hot mixture washed out with anilin and the oily filtrate transformed into phenylglycinpotassium directly by means of 110 parts of a solution containing 50 per cent. of caustic potash.

Example IV: A melt of phenylglycin ob tained as described in Example I.[ is poured while stirring into a hot solution of 69 parts of calcined sodium carbonate in 210 parts of. water. As soon as the hydrochlorate of anilin is converted in sodium chlorid and free anilin, the formed oil is separated from the aqueous solution of sodium chlorid and worked up as described in Example II.

Now what I claim and desire to secure by Letters Patent is the following:

The process for the manufacture of phenylglycin salts, consisting in totating melts, obtained in the well known manner from at least three molecular proportions of anilin and one molecular proportion of chloracetic acid, which melts contain phenylglyoinanilid besides phenylglycinanilin salt, with approximately one equivalent proportion of a neutralizing agent calculated for one molecular proportion of chloracetic acid used in the process separating the mixture of phenylglycinanilin salt and phenylglycinanilid from the metalchlorid and transforming the mixture being 'free of metal chlorid, into phenylglycinallmli salt by means of caustic alkali lye.

In testimony, that I claim the foregoing as my invent-ion, I have signed my name in presence of two witnesses, this twentieth day of January 1911.

KARL SCHNITZSPAHN.

Witnesses:

HERMANN WEIL, ROBERT 136111.. 

